Reaktion #1744548

ord-4dcc604246f344fc8cb0f19b65438f87

Reaktionsgleichung

C[C@]12CC[C@@H]3c4ccccc4CC[C@H]3[C@@H]1CCC2=O
1,3,5(10)-estratrien-17-one
CC(C)(C)[O][Al]([O]C(C)(C)C)[O]C(C)(C)C.[H-].[Li+]
lithium tri-tert.-butoxyaluminum hydride
O=C(O)C(=O)O
oxalic acid
C1CCOC1
THF
→
CC(=O)O[C@H]1CC[C@H]2[C@@H]3CCc4cc(O)ccc4[C@H]3CC[C@]12CO
17β-acetoxy-1,3,5(10)-estratriene-3,18-diol

Edukte

C[C@]12CC[C@@H]3c4ccccc4CC[C@H]3[C@@H]1CCC2=O
1,3,5(10)-estratrien-17-one
CC(C)(C)[O][Al]([O]C(C)(C)C)[O]C(C)(C)C.[H-].[Li+]
lithium tri-tert.-butoxyaluminum hydride
O=C(O)C(=O)O
oxalic acid
C1CCOC1
THF

Reagenzien

Keine

Lösungsmittel

CCOCC
ether
O
water
CO
methanol
O
water

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Sonstigeat 0° C.
  2. 2
    Extraktionis extracted with ether
  3. 3
    WaschenThe ether phase is washed neutral with water
  4. 4
    Sonstigedried
  5. 5
    Sonstigeevaporated
  6. 6
    TemperaturThe residue of crude 3,18-bis(tetrahydropyranyloxy)-1,3,5(10)-estratrien-17β-ol is heated in 1 ml
  7. 7
    workup.ADDITIONThe mixture is then introduced into water
  8. 8
    Extraktionextracted with ether
  9. 9
    Waschenwashed neutral with water
  10. 10
    SonstigeAfter drying
  11. 11
    Sonstigeevaporation
  12. 12
    Sonstigecrude 3,18-bis(tetrahydropyranyloxy)-17β-acetoxy-1,3,5(10)-estratriene is obtained
  13. 13
    Temperaturwhich is heated to the boiling point in 4 ml
  14. 14
    workup.WAITAfter 1 hour
  15. 15
    Waschenwashed neutral with water
  16. 16
    Sonstigedried
  17. 17
    Sonstigeevaporated
  18. 18
    SonstigeAfter purification by chromatography over silica gel

Vorschrift

400 mg. of 3,18-bis)tetrahydropyranyloxy)-1,3,5(10)-estratrien-17-one is mixed, in 4 ml. of absolute THF, at 0° C. with 400 mg. of lithium tri-tert.-butoxyaluminum hydride and stirred for 30 minutes at room temperature. After the mixture has been poured into water, it is extracted with ether. The ether phase is washed neutral with water, dried, and evaporated. The residue of crude 3,18-bis(tetrahydropyranyloxy)-1,3,5(10)-estratrien-17β-ol is heated in 1 ml. of pyridine with 1 ml. of acetic anhydride for 30 minutes to 100° C. The mixture is then introduced into water, stirred for 45 minutes, extracted with ether, and washed neutral with water. After drying and evaporation, crude 3,18-bis(tetrahydropyranyloxy)-17β-acetoxy-1,3,5(10)-estratriene is obtained, which is heated to the boiling point in 4 ml. of methanol with 4 ml. of water and 0.4 g. of oxalic acid. After 1 hour, the mixture is taken up in ether, washed neutral with water, dried, and evaporated. After purification by chromatography over silica gel, 17β-acetoxy-1,3,5(10)-estratriene-3,18-diol is obtained.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US03960841uspto-grants-1976_06